Method for producing fluorinated organic compounds

ABSTRACT

Disclosed are processes for the production of fluorinated olefins, preferably adapted to commercialization of CF 3 CF═CH 2  (1234yf). Three steps may be used in preferred embodiments in which a feedstock such as CCl 2 ═CClCH 2 Cl is fluorinated to synthesize a compound such as CF 3 CCl═CH 2 . The CF 3 CCl═CH 2  is preferably converted to CF 3 CFClCH 3  (244-isomer) using a SbCl 5  as the catalyst which is then transformed selectively to 1234yf. For the first step, a mixture of Cr 2 O 3  and FeCl 3 /C is preferably used as the catalyst to achieve high selectivity to CF 3 CCl═CH 2  (96%). In the second step, SbCl 5 /C is preferably used as the selective catalyst for transforming 1233xf to 244-isomer, CF 3 CFClCH 3 . The intermediates are preferably isolated and purified by distillation and used in the next step without further purification, preferably to a purity level of greater than about 95%.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No.11/619,592 filed Jan. 3, 2007, (now U.S. Pat. No. 8,084,653), which inturn claims the priority benefit of U.S. Provisional Patent ApplicationNo. 60/755,485, filed Jan. 3, 2006; and which is a Continuation-in-Partof U.S. patent application Ser. No. 11/118,503, filed on Apr. 29, 2005,(now U.S. Pat. No. 7,345,209), which in turn claims the priority benefitof U.S. Provisional Patent Application Nos. 60/567,427 and 60/567,425filed Apr. 16, 2004; and which is a Continuation-in-Part of U.S. patentapplication Ser. No. 11/118,504, filed on Apr. 29, 2005 (now U.S. Pat.No. 7,371,904), which in turn claims the priority benefit of U.S.Provisional Patent Application Nos. 60/567,426 and 60/567,429 filed Apr.16, 2004; and which is a Continuation-in-Part of U.S. patent applicationSer. No. 11/118,530, filed on Apr. 29, 2005 (now U.S. Pat. No.7,189,884), which in turn claims the priority benefit of U.S.Provisional Patent Application No. 60/567,428.

The disclosures of each of the above-mentioned applications areincorporated herein by reference. Also incorporated herein by referenceare the following U.S. Applications 60/733,378; 60/733,444; 60/733,383;60/733,355 and 60/733,379 each of which was filed on Nov. 3, 2005.

BACKGROUND OF INVENTION

(1) Field of Invention

This invention relates to novel methods for preparing fluorinatedorganic compounds, and more particularly to methods of producingfluorinated olefins.

(2) Description of Related Art

Hydrofluorocarbons (HFC's), in particular hydrofluoroalkenes suchtetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene(HFO-1234yf) and 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze)) have beendisclosed to be effective refrigerants, fire extinguishants, heattransfer media, propellants, foaming agents, blowing agents, gaseousdielectrics, sterilant carriers, polymerization media, particulateremoval fluids, carrier fluids, buffing abrasive agents, displacementdrying agents and power cycle working fluids. Unlike chlorofluorocarbons(CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentiallydamage the Earth's ozone layer, HFCs do not contain chlorine and thuspose no threat to the ozone layer.

Several methods of preparing hydrofluoroalkenes are known. For example,U.S. Pat. No. 4,900,874 (Ihara et al) describes a method of makingfluorine containing olefins by contacting hydrogen gas with fluorinatedalcohols. Although this appears to be a relatively high-yield process,for commercial scale production the handling of hydrogen gas at hightemperature raises difficult safety related questions. Also, the cost ofproducing hydrogen gas, such as building an on-site hydrogen plant, canbe in many situations prohibitive.

U.S. Pat. No. 2,931,840 (Marquis) describes a method of making fluorinecontaining olefins by pyrolysis of methyl chloride andtetrafluoroethylene or chlorodifluoromethane. This process is arelatively low yield process and a very large percentage of the organicstarting material is converted in this process to unwanted and/orunimportant byproducts.

The preparation of HFO-1234yf from trifluoroacetylacetone and sulfurtetrafluoride has been described. See Banks, et al., Journal of FluorineChemistry, Vol. 82, Iss. 2, p. 171-174 (1997). Also, U.S. Pat. No.5,162,594 (Krespan) discloses a process wherein tetrafluoroethylene isreacted with another fluorinated ethylene in the liquid phase to producea polyfluoroolefin product.

SUMMARY

Applicants have discovered a method for producing fluorinated organiccompounds, including hydrofluoropropenes, which preferably comprisesconverting at least one compound of Formula (I):C(X)_(m)CCl(Y)_(n)C(X)_(m)  (I)to at least one compound of Formula (II)CF₃CF═CHZ  (II)where each X, Y and Z is independently H, F, Cl, I or Br, and each m isindependently 1, 2 or 3, and n is 0 or 1. As used herein and throughout,unless specifically indicated otherwise, the term “converting” includesdirectly converting (for example, in a single reaction or underessentially one set of reaction conditions, an example of which isdescribed hereinafter) and indirectly converting (for example, throughtwo or more reactions or using more than a single set of reactionconditions).

In certain preferred embodiments of the invention, the compound ofFormula (I) comprises a compound wherein n is 0, each X is independentlyH or Cl, and Z is H. Such preferred embodiments include converting atleast one C3 alkene in accordance with Formula (IA):C(X)₂═CClC(X)₃  (IA)to at least one compound of formula (II)CF₃CF═CHZ  (II)where each X is independently H or Cl. Preferably the one or morecompounds of Formula (IA) are tetrachloropropene(s), and are even morepreferably selected from the group consisting of CH₂═CClCCl₃,CCl₂═CClCH₂Cl, CHCl═CClCCl₂H, and combinations of these.

In certain preferred embodiments of the invention the compound ofFormula (I) comprises a compound wherein n is 0 and the terminalsaturated carbon has three (3) F substituents. Such preferredembodiments include converting at least one C3 alkene in accordance withFormula (IAA):C(X)₂═CClCF₃  (IAA)to at least one compound of formula (II)CF₃CF═CHZ  (II)where each X is independently H or Cl. Preferably the one or morecompounds of Formula (IAA) are trifluoropropene(s). Included in thepreferred trifluorpropene compounds of the present invention isCH₂═CClCF₃ (HCFC-1223xf).

In certain preferred embodiments the compound of Formula (I) comprises acompound wherein n is 1 and each X and Y is independently H, F or Cl.Such embodiments include converting at least one C3 alkane of Formula(IB):C(X)₃CClYC(X)₃  (IB)to at least one compound of formula (II)CF₃CF═CHZ  (II)where each X and Y is independently H, F or Cl. In certain preferredembodiments, the Formula (IB) compound has at least two haologens on oneterminal carbon and at least two hydrogen atoms on the other terminalcarbon. Preferably the compounds of Formula (IB) contain at least fourhalogen substituents and even more preferably at least five halogensubstituents. In certainly highly preferred embodiments, the conversionstep of the present invention comprises converting a compound of Formula(IB) wherein Y is F and all three X on one terminal carbon are F.Preferably the compound of Formula (IB) is a penta-halogenated propane,preferably with at least four fluorine substituents. Even morepreferably the penta-halogenated propane of Formula (IB) comprises atetra-fluorinated, mono-chlorinated propane, includingchlorotetrafluoropropane (C₃H₃F₄Cl), including all isomers thereof, suchas 1,1,1,2-tetrafluoro-2-chloropropane and1-chloro-1,3,3,3-tetrafluoropropane (HFC-244fa). Other preferredpenta-halogenated compounds of Formula (IB) include CH₂ClCHClCCl₃,CHCl₂CCl₂CH₂Cl, CHCl₂CHClCHCl₂. Of course, combinations of compounds ofFormula (I), including combinations of compounds of Formulas (IA), (IAA)and (IB) may be used.

In certain preferred embodiments, the step of converting a compound ofFormula (I) to at least one compound of Formula (II) comprises directlyconverting a compound of Formula (I). In other embodiments, the step ofconverting a compound of Formula (I) to at least one compound of Formula(II) comprises indirectly converting a compound of Formula (I).

An example of indirect conversion embodiments includes converting acompound of Formula (IA) to a compound of Formula (IAA), then convertingsaid Formula (IAA) compound to a Formula (IB) compound, and thenconverting the Formula (IB) to the Formula (II) compound. In certainmore specific indirect conversion embodiments, the step of converting acompound of Formula (I) comprises providing at least onemonchlortrifluorpropene in accordance with Formula (IAA), preferablyCF₃CCl═CH₂ (HFO-1233xf) and reacting said monchlortrifluorpropene underconditions effective to produce at least one monchlortetrafluorpropanein accordance with Formula (IB), preferably CF₃CFClCH₃ (HFC-244bb),which in turn is preferably exposed to reaction conditions effective toproduce at least one compound in accordance with Formula (II),preferably HFO-1234yf. In preferred embodiments said exposing stepcomprises conducting one or more of said reactions in a gas phase in thepresence of a catalyst, preferably a metal-based catalyst. Examples ofsuch preferred conversion steps are disclosed more fully hereinafter. Ofcourse, it is contemplated that in the broad scope of the invention thatany of the Formula (I) compounds may be converted, directly orindirectly, to a compound of Formula (II) in view of the teachingscontained herein.

In certain preferred embodiments the converting step comprises exposingthe compound of Formula (I), and preferably Formula (1A), (IAA) orFormula (1B), to one or more sets of reaction conditions effective toproduce at least one compound in accordance with Formula (II). It iscontemplated that in certain embodiments the exposing step comprisesreacting said one or more compound(s) of Formula (IA) or (IAA) underconditions effective to produce chlorofluoropropane, more preferably apropane in accordance with Formula (IBB):CF₃CClFC(X)₃  Formula (IBB)where each X is independently F, Cl or H. In certain preferredembodiments, at least one of said X in Formula (IBB) is H, and even morepreferably all three X are H.

The preferred conversion step of the present invention is preferablycarried out under conditions, including the use of one or morereactions, effective to provide a Formula (I) conversion of at leastabout 50%, more preferably at least about 75%, and even more preferablyat least about 90%. In certain preferred embodiments the conversion isat least about 95%, and more preferably at least about 97%. Further incertain preferred embodiments, the step of converting the compound ofFormula (I) to produce a compound of Formula (II) is conducted underconditions effective to provide a Formula (II) yield of at least about75%, more preferably at least about 85%, and more preferably at leastabout 90%. In certain preferred embodiments a yield of about 95% orgreater is achieved.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

One beneficial aspect of the present invention is that it enables theproduction of desirable fluroolefins, preferably C3 fluoroolefins, usingrelatively high conversion and high selectivity reactions. Furthermore,the present methods in certain preferred embodiments permit theproduction of the desirable fluoroolefins, either directly orindirectly, from relatively attractive starting materials. For example,2-chloro, 2,3,3,3-tetrafluoropropane is a compound that may in certainembodiments be an advantageous starting material because such productsare relatively easy to handle.

Preferably the Formula (I) compound is exposed to reaction conditionseffective to produce a reaction product containing one or more of thedesired fluorolefins, preferably one or more compounds of Formula (II).Although it is contemplated that the exposure step in certainembodiments may effectively be carried out in a single reaction stageand/or under a single set of reaction conditions, as mentioned above, itis preferred in many embodiments that the conversion step comprise aseries of reaction stages or conditions. In one preferred aspect of thepresent invention, the conversion step comprises: (a) reacting acompound of Formula (I) which is not a compound of Formula (IAA),preferably a compound of Formula (IA), in a gas and/or liquid phasereaction in the presence of at least a first catalyst to produce atleast one compound of Formula (IAA), such as amonochloro-trifluoro-propene, preferably HFO-1233xf; (b) reacting the atleast one monochloro-trifluoro-propene compound, in a gas and/or liquidphase and preferably in the presence of at least a catalyst, preferablya second catalyst which is different than the first catalyst, to produceat least one compound of Formula (IB) and even more preferably Formula(IBB), such as monochloro-terafluoro-propane; and (c) reacting saidcompound of Formula (IB), in a gas and/or liquid phase, to produce thedesired HFO, preferably HFO-1234yf. Each of the preferred reaction stepsis described in detail below, with the headings being used forconvenience but not necessarily by way of limitation.

I. Fluorination of the Compound of Formula I(A)

One preferred reaction step in accordance with the present invention maybe described by those reactions in which the compound of Formula (IA) isfluorinated to produce a compound of Formula (IAA). In certain preferredembodiments, especially embodiments in which the compound of Formula(IA) comprises C(X)₂═CClC(X)₃, where each X is independently H or Cl,the present converting step comprises first reacting said compound(s) byfluorinating said compound(s), preferably with HF in a gas phase, toproduce an HFO that is at least trifluorinated, such as HFO-1223xf.Preferably this gas phase reaction is at least partially catalyzed.

The preferred fluorination of the compound of Formula (IA) is preferablycarried out under conditions effective to provide a Formula (IA)conversion of at least about 50%, more preferably at least about 75%,and even more preferably at least about 90%. In certain preferredembodiments the conversion is at least about 95%, and more preferably atleast about 97%. Further in certain preferred embodiments, theconversion of the compound of Formula (IA) comprises reacting suchcompound under conditions effective to produce at least one compound ofFormula (IAA), such as monochlorotrifluoropropene (preferably CF₃CCl═CH₂(HFO-1233xf)) at a selectivity of at least about 50%, more preferably atleast about 70%, more preferably at least about 80%, and even morepreferably at least about 90%, with selectivities of about 95% orgreater being achieved in certain embodiments.

In general, it is possible that the fluorination reaction step can becarried out in the liquid phase or in the gas phase, or in a combinationof gas and liquid phases, and it is contemplated that the reaction canbe carried out batch wise, continuous, or a combination of these.

For embodiments in which the reaction comprises a liquid phase reaction,the reaction can be catalytic or non-catalytic. Preferably, a catalyticprocess is used. Lewis acid catalyst, such as metal-halide catalysts,including antimony halides, tin halides, thallium halides, iron halides,and combinations of two or more of these, are preferred in certainembodiments. Metal chlorides and metal fluorides are particularlypreferred. Examples of particularly preferred catalysts of this typeinclude SbCl₅, SbCl₃, SbF₅, SnCl₄, TiCl₄, FeCl₃ and combinations of twoor more of these.

In preferred gas phase fluorination of Formula (I) compounds, preferablyFormula (IA) compounds, the reaction is at least partially a catalyzedreaction, and is preferably carried out on a continuous basis byintroducing a stream containing the compound of Formula (I), preferablyFormula (IA), into one or more reaction vessels, such as a tubularreactor. In certain preferred embodiments, the stream containing thecompound of Formula (I), and preferably Formula (IA), is preheated to atemperature of from about 80° C. to about 400° C., more preferably fromabout 150° C. to about 400° C., and in certain embodiments preferablyabout 300° C., and introduced into a reaction vessel (preferably a tubereactor), which is maintained at the desired temperature, preferablyfrom about 80° C. to about 700° C., more preferably from about 90° C. toabout 600° C., even more preferably in certain embodiments from about400° C. to about 600° C., more preferably from about 450° C. to about600° C., where it is preferably contacted with catalyst and fluorinatingagent, such as HF.

Preferably the vessel is comprised of materials which are resistant tocorrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.

Preferably the vessel contains catalyst, for example a fixed or fluidcatalyst bed, packed with a suitable fluorination catalyst, withsuitable means to ensure that the reaction mixture is maintained withthe desired reaction temperature range.

Thus, it is contemplated that the fluorination reaction step may bepreformed using a wide variety of process parameters and processconditions in view of the overall teachings contained herein. However,it is preferred in certain embodiments that this reaction step comprisea gas phase reaction, preferably in the presence of catalyst, and evenmore preferably a chromium-based catalyst (such as Cr₂O₃ catalyst), aniron-based catalyst (such as FeCl₃ on carbon (designated herein asFeCl₃/C for convenience), and combinations of these. In preferredembodiments, the catalyst is a combination of the two aforementionedcatalysts, where the reaction vessel contains in a first zone thechromium-based catalyst and in a second zone the iron-based catalyst.The temperature of the reaction in the chromium-based catalyst reactionis preferably kept at a temperature of from about 200° C. to about 600°C. and even more preferably from about 250° C. to about 500° C. Thetemperature of the reaction in the iron-based catalyst reaction zone ispreferably kept at a temperature of from about 80° C. to about 300° C.and even more preferably from about 100° C. to about 250° C.

In general it is also contemplated that a wide variety of reactionpressures may be used for the fluorination reaction, depending again onrelevant factors such as the specific catalyst being used and the mostdesired reaction product. The reaction pressure can be, for example,superatmospheric, atmospheric or under vacuum and in certain preferredembodiments is from about 1 to about 200 psia, and in certainembodiments from about 1 to about 120 psia.

In certain embodiments, an inert diluent gas, such as nitrogen, may beused in combination with the other reactor feed(s).

It is contemplated that the amount of catalyst use will vary dependingon the particular parameters present in each embodiment.

II. Fluorination of the Compound of Formula I(AA)

The compound of Formula (IAA), preferably produced as described above,and then is preferably subject to further fluorination reaction(s) toproduce a compound of Formula (IB), such as HCFC-244. Preferably thisgas phase reaction is at least partially catalyzed.

The fluorination of the compound of Formula (IAA) is preferably carriedout under conditions effective to provide a Formula (IAA) conversion ofat least about 40%, more preferably at least about 50%, and even morepreferably at least about 60%. Further in certain preferred embodiments,the conversion of the compound of Formula (IA) comprises reacting suchcompound under conditions effective to produce at least onemonochlorotetrafluoropropane, preferably HCFC-244, at a selectivity ofat least about 70%, more preferably at least about 80%, and even morepreferably at least about 85%, with selectivities of about 90% orgreater being achieved in certain embodiments.

In general, it is possible that this fluorination reaction step can becarried out in the liquid phase or in the gas phase, or in a combinationof gas and liquid phases, and it is contemplated that the reaction canbe carried out batch wise, continuous, or a combination of these.

For embodiments in which the reaction comprises a liquid phase reaction,the reaction can be catalytic or non-catalytic. Preferably, a catalyticprocess is used. Lewis acid catalyst, such as metal-halide catalysts,including antimony halides, tin halides, thallium halides, iron halides,and combinations of two or more of these, are preferred in certainembodiments. Metal chlorides and metal fluorides are particularlypreferred. Examples of particularly preferred catalysts of this typeinclude SbCl₅, SbCl₃, SbF₅, SnCl₄, TiCl₄, FeCl₃ and combinations of twoor more of these.

In preferred gas phase fluorination of Formula (IAA) compounds, thereaction is at least partially a catalyzed reaction, and is preferablycarried out on a continuous basis by introducing a stream containing thecompound of Formula (IAA) into one or more reaction vessels, such as atubular reactor. In certain preferred embodiments, the stream containingthe compound of Formula (I), and preferably Formula (IAA), is preheatedto a temperature of from about 50° C. to about 400° C., and in certainembodiments preferably about 80° C. In other embodiments, it ispreferred that the stream containing the compound of Formula (I), andpreferably Formula (IAA), is preheated to a temperature of from about150° C. to about 400° C., preferably about 300° C. This steam,preferably after preheating, is then preferably introduced into areaction vessel (preferably a tube reactor), which is maintained at thedesired temperature, preferably from about 50° C. to about 250° C., morepreferably from about 50° C. to about 150° C., where it is preferablycontacted with catalyst and fluorinating agent, such as HF.

Preferably the vessel is comprised of materials which are resistant tocorrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.

Preferably the vessel contains catalyst, for example a fixed or fluidcatalyst bed, packed with a suitable fluorination catalyst, withsuitable means to ensure that the reaction mixture is maintained withinabout the desired reaction temperature range.

Thus, it is contemplated that the fluorination reaction step may bepreformed using a wide variety of process parameters and processconditions in view of the overall teachings contained herein. However,it is preferred in certain embodiments that this reaction step comprisea gas phase reaction, preferably in the presence of catalyst, and evenmore preferably an Sb-based catalyst, such as catalyst which is about 50wt % SbCl₅/C. Other catalysts which may be used include: from about 3 toabout 6 wt % FeCl₃/C; SbF₅/C; about 20 wt % SnCl₄/C; about 23 wt %TiCl₄/C; and activated carbon. Preferably the catalyst comprises Cl₂ andHF pre-treated SbCl₅/C.

In general it is also contemplated that a wide variety of reactionpressures may be used for the fluorination reaction, depending again onrelevant factors such as the specific catalyst being used and the mostdesired reaction product. The reaction pressure can be, for example,superatmospheric, atmospheric or under vacuum and in certain preferredembodiments is from about 1 to about 200 psia, more preferably incertain embodiments from about 1 to about 120 psia.

In certain embodiments, an inert diluent gas, such as nitrogen, may beused in combination with the other reactor feed(s).

It is contemplated that the amount of catalyst use will vary dependingon the particular parameters present in each embodiment.

III. Dehydrohalogenation of Formula (IB)

One preferred reaction step in accordance with the present invention maybe described by those reactions in which the compound of Formula (IB) isdehydrohalogenated to produce a compound of Formula (II). In certainpreferred embodiments, the stream containing the compound of Formula(IB), and preferably Formula (IBB) is preheated to a temperature of fromabout 150° C. to about 400° C., preferably about 350° C., and introducedinto a reaction vessel, which is maintained at about the desiredtemperature, preferably from about 200° C. to about 700° C., morepreferably from about 300° C. to about 700° C., more preferably fromabout 300° C. to about 450° C., and more preferably in certainembodiments from about 350° C. to about 450° C.

Preferably the vessel is comprised of materials which are resistant tocorrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.Preferably the vessel contains catalyst, for example a fixed or fluidcatalyst bed, packed with a suitable dehydrohalogenation catalyst, withsuitable means to heat the reaction mixture to about the desiredreaction temperature.

Thus, it is contemplated that the dehydrohalogenation reaction step maybe preformed using a wide variety of process parameters and processconditions in view of the overall teachings contained herein. However,it is preferred in certain embodiments that this reaction step comprisea gas phase reaction, preferably in the presence of catalyst, and evenmore preferably a carbon- and/or metal-based catalyst, preferablyactivated carbon, a nickel-based catalyst (such as Ni-mesh) andcombinations of these. Other catalysts and catalyst supports may beused, including palladium on carbon, palladium-based catalyst (includingpalladium on aluminum oxides), and it is expected that many othercatalysts may be used depending on the requirements of particularembodiments in view of the teachings contained herein. Of course, two ormore any of these catalysts, or other catalysts not named here, may beused in combination.

The gas phase dehydrohalogenation reaction may be conducted, forexample, by introducing a gaseous form of a compound of Formula (TB)into a suitable reaction vessel or reactor. Preferably the vessel iscomprised of materials which are resistant to corrosion as Hastelloy,Inconel, Monel and/or fluoropolymers linings. Preferably the vesselcontains catalyst, for example a fixed or fluid catalyst bed, packedwith a suitable dehydrohalogenation catalyst, with suitable means toheat the reaction mixture to about the desired reaction temperature.

While it is contemplated that a wide variety of reaction temperaturesmay be used, depending on relevant factors such as the catalyst beingused and the most desired reaction product, it is generally preferredthat the reaction temperature for the dehydrohalogentation step is fromabout 200° C. to about 800° C., more preferably from about 400° C. toabout 800° C., and even more preferably from about 400° C. to about 500°C., and more preferably in certain embodiments from about 300° C. toabout 500° C.

In general it is also contemplated that a wide variety of reactionpressures may be used, depending again on relevant factors such as thespecific catalyst being used and the most desired reaction product. Thereaction pressure can be, for example, superatmospheric, atmospheric orunder vacuum, and in certain preferred embodiments is from about 1 toabout 200 psia, and even more preferably in certain embodiments fromabout 1 to about 120 psia.

In certain embodiments, an inert diluent gas, such as nitrogen, may beused in combination with the other reactor feed(s). When such a diluentis used, it is generally preferred that the compound of Formula (I),preferably Formula (IB), comprise from about 50% to greater than 99% byweight based on the combined weight of diluent and Formula (I) compound.

It is contemplated that the amount of catalyst use will vary dependingon the particular parameters present in each embodiment.

Preferably in such dehydrofluorination embodiments as described in thissection, the conversion of the Formula (IB) compound is at least about60%, more preferably at least about 75%, and even more preferably atleast about 90%. Preferably in such embodiments, the selectivity tocompound of Formula (II), preferably HFO-1234yf, is at least about 50%,more preferably at least about 70% and more preferably at least about80%.

EXAMPLES

Additional features of the present invention are provided in thefollowing examples, which should not be construed as limiting the claimsin any way.

Example 1 Preparation of CH₂═CClCH₂Cl (2,3-Dichloro-1-propene) fromCH₂ClCHClCH₂Cl

About 8500 grams of 1,2,3-trichloropropane and about 88.0 grams Aliquat336 were charged into a 30 liter glass vessel, equipped with TEFLON®shaft and stir blades, heated with internal TEFLON® coated copper coilsand refrigerant/heating circulation bath and refrigerated condenser. Themixture was then heated to about 73° C. with medium speed agitation. Atthis temperature, about 10,000 grams of 25 wt % NaOH/H2O solution isadded into the reactor from a separate container over a 2 hour period oftime. The pH was kept at about 14. After addition, the reaction progresswas monitored by GC and GC/MS. The conversion of 1,2,3-trichloropropanewas about 97.5% and the selectivity to CH₂═CClCH₂Cl was about 95.4%.After the stipulated reaction time, the mixture was cooled and about 4.0liters of distilled and ionized water was added into the mixture. Themixture was stirred for about 10 minutes and allowed to separate. Thelower layer product (boiling point of about 92.5° C.) was drained anddistilled to substantially isolate and purify product. The crude yieldbefore distillation was about 6408 grams (GC purity of about 93%).

Example 2 Preparation of HCCl₂CCl₂CH₂Cl from CH₂═CClCH₂Cl

Chlorine was bubbled into about 82.4 g of 2,3-dichloropropene at about10 to about 30° C. with the aid of ice bath cooling until a pale yellowcolor persisted for about 45 minutes. The crude product in an amount ofabout 130.4 g, consisted of about 93.6% CH₂ClCCl₂CH₂Cl and about 2.6%2,3-dichloropropene.

Five hundred grams of CH₂ClCCl₂CH₂Cl was charged into a photoreactor.The jacket for the reactor as well as the jacket for the 450 W UV lampwere cooled to about 15° C. using a circulating cooling bath. A total ofabout 150 g of chlorine was bubbled into the organic liquid over aperiod of about 2 hours. The crude product weighed about 591 g. GCanalysis indicated a conversion of about 54.4% and selectivity for thedesired HCCl₂CCl₂CH₂Cl of about 87%. Distillation providedHCCl₂CCl₂CH₂Cl in 99% purity.

Example 3 Preparation of CCl₂═CClCH₂Cl from HCCl₂CCl₂CH₂Cl

Aliquat-336® (about 0.26 g) and about 24.8 g of HCCl₂CCl₂CH₂Cl werestirred rapidly at room temperature while adding about 20 g of 25%aqueous NaOH over 19 minutes. Stirring was continued overnight beforeadding 30 mL water and allowing the phases to separate. The lowerorganic phase, in an amount of about 19.8 g, was about 97.5% pureCCl₂═CClCH₂Cl by GC analysis (96% yield). Prior to fluorination, it wasdistilled (bp about 69 to about 72° C. at about 30 mm Hg) to remove anyphase transfer catalyst. H NMR: δ 4.41 (s) ppm.

Example 4 Selective Catalyzed-Transformation of CCl₂═CClCH₂Cl toCF₃CCl═CH₂ (HFO-1233xf) in Gas-Phase

An 22-inch long and ½-inch diameter Monel pipe gas-phase reactor ischarged with about 120 cc of a catalyst or a mixture of two catalysts.In case of a mixture, Cr₂O₃ catalyst is kept at the bottom zone of thereactor at a constant temperature of about 270° C.-500° C. and the othercatalyst, such as FeCl₃/C, is kept at the middle and the top zone of thereactor at a constant temperature of about 120° C.-220° C. The reactoris mounted inside a heater with three zones (top, middle, and bottom).The reactor temperature is read by custom-made-5-point thermocoupleskept inside at the middle of the reactor. The bottom of the reactor isconnected to a pre-heater, which is kept at 300° C. by electricalheating. The liquid-HF is fed from a cylinder into the pre-heaterthrough a needle valve, liquid mass-flow meter, and a research controlvalve at a constant flow of about 1 to about 1000 grams pre hour (g/h).The HF cylinder is kept at a constant pressure of 45 psig by applyinganhydrous N₂ gas pressure into the cylinder head space. About 10 toabout 1000 g/h of CCl₂═CClCH₂Cl is fed as a liquid through a dip tubefrom a cylinder under about 45 psig of N₂ pressure. The organic flowsfrom the dip tube to the preheater (kept at about 250° C.) through aneedle valve, liquid mass-flow meter, and a research control valve at aconstant flow of 1-1000 g/h. The organic is also fed as a gas whileheating the cylinder containing organic at about 220° C. The gas comingout of the cylinder is passed through a needle valve and a mass flowcontroller into the preheater. The organic line from the cylinder to thepre-heater is kept at about 200° C. by wrapping with constanttemperature heat trace and electrical heating elements. All feedcylinders are mounted on scales to monitor their weight by difference.The catalysts are dried at the reaction temperature over a period ofabout 8 hours and then pretreated with about 50 g/h of HF underatmospheric pressure over a period of about 6 hours and then under 50psig HF pressure over another period of about 6 hours before contactingwith organic feed containing CCl₂═CClCH₂Cl. The reactions are run at aconstant reactor pressure of about 0 to about 150 psig by controllingthe flow of reactor exit gases by another research control valve. Thegases exiting reactor are analyzed by on-line GC and GC/MS connectedthrough a hotbox valve arrangement to prevent condensation. Theconversion of CCl₂═CClCH₂Cl is about 70 to about 100% and theselectivity to 1233xf is about 80% to about 95%, respectively. Theproduct is collected by flowing the reactor exit gases through ascrubber solution comprising about 20 wt % to about 60 wt %. KOH inwater and then trapping the exit gases from the scrubber into a cylinderkept in dry ice or liquid N₂. The product, 1233xf is then substantiallyisolated by distillation. The results are tabulated in Table 1.

TABLE 1 Transformation of CCl₂═CClCH₂Cl to CF₃CCl═CH₂ (CCl₂═CClCH₂Cl +3HF → CF₃CCl═CH₂ + 3HCl) T, HF flow, CCl₂═CClCH₂Cl % Conv of % Sel to #Catalyst ° C. g/h flow, g/h CCl₂═CClCH₂Cl 1233xf 1 10% v/v Cr₂O₃-350/150 50 12 79 81 90% v/v FeCl₃/C 2 20% v/v Cr₂O₃- 350/150 50 12 83 8680% v/v FeCl₃/C 3 30% v/v Cr₂O₃- 350/150 50 12 89 96 70% v/v FeCl₃/C 430% v/v Cr₂O₃- 350/150 70 12 79 93 70% v/v FeCl₃/C 5 30% v/v Cr₂O₃-345/170 50 25 85 90 70% v/v FeCl₃/C 6 Cr₂O₃ 350 50 20 90 93 7 FeCl₃/C150 50 20 74 39 8 SbCl₅/C 150 50 20 81 52 Reaction conditions: Catalystused (total) 120 cc; pressure, 1.5 psig;

Examples 5A and 5B Liquid-Phase Catalytic Fluorination of CF₃CCl═CH₂(1233xf) with HF to CF₃CFClCH₃ (244bb) Example 5A

About 327 grams of HF, about 50 grams 1233xf, and about 75 grams SbCl₅were charged into a 1-L autoclave. The reaction mixture was stirred at atemperature of about 80° C. for about 3 hours under about 620 psig ofpressure. After the reaction, the reactor was cooled to about 0° C. andabout 300 ml water was then added slowly into the autoclave over aperiod of about 45 min. After complete addition of water under stirring,the reactor was cooled to room temperature and then the overhead gaseswere transferred to another collecting cylinder. The yield of CF₃CFClCH₃was about 90% at a 1233xf conversion level of about 98%. The other majorby-products were CF₃CF₂CH₃ (2%), and an unidentified isomer of a C4compound of the general formula, C₄H₃Cl₃F₄ (8%).

Example 5B

About 327 grams HF, about 50 grams 1233xf, and about 75 grams SbCl₅ werecharged into a 1-L autoclave. The reaction mixture was stirred at 80° C.for about 3 hours under about 625 psig of pressure. After the reaction,the reactor was cooled to about 45° C. and then the overhead gas mixturewas passed through a well dried KF, NaF, or Al₂O₃ (350 g) packed columnkept at about 80° C. to strip off HF from the gas stream. The gasescoming out of the column are collected in a cylinder kept in dry ice(−70° C.) bath. The yield of CF₃CFClCH₃ was 87% at a 1233xf conversionlevel of 93%. The other major by-products were CF₃CF₂CH₃ (1%), and anunidentified isomer of a C4 compound of the general formula, C₄H₃Cl₃F₄(7%). The product, CF₃CFClCH₃ was isolated by distillation with 98%purity.

Example 6 Gas-Phase Catalytic Fluorination of CF₃CCl═CH₂ (1233xf) withHF to CF₃CFClCH₃ (244bb)

A 22-inch (½-inch diameter) Monel tube gas phase reactor was chargedwith about 120 cc of a catalyst. The reactor was mounted inside a heaterwith three zones (top, middle and bottom). The reactor temperature wasread by a custom made 5-point thermocouple kept at the middle inside ofthe reactor. The inlet of the reactor was connected to a pre-heater,which was kept at about 300° C. by electrical heating. Organic (1233xf)was fed from a cylinder kept at 70° C. through a regulator, needlevalve, and a gas mass-flow-meter. The organic line to the pre-heater washeat traced and kept at a constant temperature of about 73° C. byelectrical heating to avoid condensation. N₂ was used as a diluent insome cases and fed from a cylinder through a regulator and a mass flowcontroller into the pre-heater. All feed cylinders were mounted onscales to monitor their weight by difference. The reactions were run ata constant reactor pressure of from about 0 to about 100 psig bycontrolling the flow of reactor exit gases by another research controlvalve. The gas mixtures exiting reactor was analyzed by on-line GC andGC/MS connected through a hotbox valve arrangements to preventcondensation. The conversion of 1233xf was from about 50% to about 65%and the selectivity to 244 isomer (CF₃CFClCH₃) was from about 90% toabout 93% depending on the reaction conditions using 120 cc of 50 wt %SbCl₅/C as the catalyst at about 65° C. to about −85° C. with a HF flowof about 50 g/h and organic flow of about 15 g/h. No CF₃CF₂CH₃ wasobserved under the reaction conditions. The catalyst is pretreated atfirst with 50 g/h HF at about 65° C. for about 2 hours and then withabout 50 g/h HF and about 200 sccm of Cl₂ at about 65° C. for about 4hours. After pre-treatment, about 50 sccm of N₂ is flows over a periodof about 40 minutes through the catalyst bed to sweep free chlorine fromthe catalyst surface prior to interacting with the organic feed(1233xf). Pretreatment is considered important to many embodiments ofthe invention. The products were collected by flowing the reactor exitgases through a 20-60 wt % aqueous KOH scrubber solution and thentrapping the exit gases from the scrubber into a cylinder kept in dryice or liquid N₂. The products were then isolated by distillation. About50 wt % SbCl₅/C, about 3 to about 6 wt % FeCl₃/C, 20 wt % SnCl₄/C, andabout 23 wt % TiCl₄/C, using 4 different kind of activated carbon suchas Shiro saga, Calgon, Norit, and Aldrich were used as the catalyst atfrom about 60 to about 150° C. Among all the catalysts used for thisreaction, Cl₂ and HF pre-treated SbCl₅/C was found to be generallypreferred in terms of activity. The results using SbCl₅ as the catalystare shown in Table 2.

TABLE 2 Catalyzed-gas-phase transformation of CF₃CCl═CH₂ to CF₃CFClCH₃Conv. of T, CF₃CCl═CH₂ Sel. to # Cat ° C. (1233xf) CF₃CFClCH₃ 1 10 wt %SbCl₅/C 60 15 100 2 20 wt % SbCl₅/C 60 21 98 3 30 wt % SbCl₅/C 60 32 984 50 wt % SbCl₅/C 60 55 97 5 50 wt % SbCl₅/C 80 62 93 6 50 wt % SbCl₅/C100 56 87 7 60 wt % SbCl₅/C 60 59 91 8 50 wt % SbCl₅/NORIT 60 34 92 RFC3 Activated Carbon 9 50 wt % SbCl₅/Shiro Saga 60 56 96 Activated Carbon10 50 wt % SbCl₅/Aldrich 60 57 94 Activated Carbon Reaction conditions:1233xf flow, 150 sccm; HF flow 50 g/h; pressure, 2.5-5.3 psig; in 1-5reactions Calgon activated carbon is used as the catalyst support;catalyst, 120 cc. All catalysts are pre-treated with Cl₂ and HF prior tocontacting with 1233xf.

Example 7 Conversion of CF₃CFClCH₃ to CF₃CF═CH₂ in Gas-Phase

A 22-inch (½-inch diameter) Monel tube gas phase reactor was chargedwith 120 cc of catalyst. The reactor was mounted inside a heater withthree zones (top, middle and bottom). The reactor temperature was readby custom made 5-point thermocouples kept at the middle inside of thereactor. The inlet of the reactor was connected to a pre-heater, whichwas kept at about 300° C. by electrical heating. Organic (CF₃CFClCH₃)was fed from a cylinder kept at about 65° C. through a regulator, needlevalve, and a gas mass-flow-meter. The organic line to the pre-heater washeat traced and kept at a constant temperature of from about 65° C. toabout 70° C. by electrical heating to avoid condensation. The feedcylinder was mounted on scales to monitor their weight by difference.The reactions were run at a constant reactor pressure of from about 0 toabout 100 psig by controlling the flow of reactor exit gases by anotherresearch control valve. The gas mixture exiting reactor was analyzed byon-line GC and GC/MS connected through a hotbox valve arrangement toprevent condensation. The conversion of CF₃CFClCH₃ was almost 98% andthe selectivity to HFO-1234yf was from about 69% to about 86% dependingon the reaction conditions. The products were collected by flowing thereactor exit gases through a about 20 wt % to about 60 wt % of aquesousKOH scrubber solution and then trapping the exit gases from the scrubberinto a cylinder kept in dry ice or liquid N₂. The products were thenisolated by distillation. Results are tabulated in Table 3.

TABLE 3 Catalyzed-transformation of CF₃CFClCH₃ to HFO-1234yf Flow rate,CF₃CFClCH₃ T, (244 isomer) Conversion 1234yf # Cat ° C. sccm of 244(Sel. %) 1 A 400 150 100 46 2 B 400 150 96 63 3 C 400 100 100 64 4 D 400100 99 93 5 D 400 150 92 89 6 E 400 100 96 56 7 F 400 100 87 51 8 G 400100 100 37 Reaction conditions: pressure, 2.5-5.3 psig; catalyst, 100cc, A is NORIT RFC 3; B is Shiro-Saga activated carbon; C is Aldrichactivated carbon; D is Calgon activated carbon; activated carbon; E is0.5 wt % Pd/C; F is 0.5 wt % Pt/C; G is Ni-mesh; Organic cylindertemperature-65° C.; CF₃CFClCH₃ (244) line to the preheater-60° C.;Preheater, 350° C.; P-5 psig.

Example 8 Selective Catalyzed-Transformation of CCl₃CCl═CH₂ toCF₃CCl═CH₂ (HFO-1233xf) in Gas-Phase

A 22-inch long and ½-inch diameter Monel pipe gas phase reactor wascharged with 120 cc of a catalyst or a mixture of two catalysts. In caseof a mixture, Cr₂O₃ catalyst is kept at the bottom zone of the reactorat a substantially constant temperature of from about 270° C. to about500° C. and the other catalyst, such as FeCl₃/C is kept at the middleand the top zone of the reactor at a substantially constant temperatureof from about 120° C. to about 220° C. The reactor was mounted inside aheater with three zones (top, middle, and bottom). The reactortemperature was read by custom-made-5-point thermocouples kept inside atthe middle of the reactor. The bottom of the reactor was connected to apre-heater, which was kept at about 300° C. by electrical heating. Theliquid-HF was fed from a cylinder into the pre-heater through a needlevalve, liquid mass-flow meter, and a research control valve at asubstantially constant flow of from about 1 to about 1000 g/h. The HFcylinder was kept at a substantially constant pressure of about 45 psigby applying anhydrous N₂ gas pressure into the cylinder head space. Afeed rate of from about 10 g/h to about 1000 g/h of CCl₃CCl═CH₂ was fedas a liquid through a dip tube from a cylinder under about 45 psig of N₂pressure. The organic was flown from the dip tube to the pre-heater(kept at about 250° C.) through needle valve, liquid mass-flow meter,and a research control valve at a substantially constant flow of fromabout 1 to about 1000 g/h. The organic is also fed as a gas whileheating the cylinder containing organic at about 220° C. The gaseffluent from the cylinder is passed through a needle valve and a massflow controller into the pre-heater. The organic line from the cylinderto the pre-heater was kept at about 200° C. by wrapping with constanttemperature heat trace and electrical heating elements. All feedcylinders were mounted on scales to monitor their weight by difference.The catalysts were dried at the reaction temperature over a period ofabout 8 hours and then pretreated with about 50 g/h of HF underatmospheric pressure over a 6 hour period and then under about 50 psigHF pressure over a 6 hour period before contacting with organic feed,CCl₃CCl═CH₂. The reactions were run at a substantially constant reactorpressure ranging from about 0 to about 150 psig by controlling the flowof reactor exit gases by another research control valve. Those gasesexiting reactor were analyzed by on-line GC and GC/MS connected througha hotbox valve arrangements to prevent condensation. The conversion ofCCl₃CCl═CH₂ was in a range of from about 90% to about 100% and theselectivity to CF₃CCl═CH₂ (1233xf) was about 79%. The effluent containedin addition HFO-1243zf in an amount of about 7.7%, 1232-isomer in anamount of about 1.3%, and 1223 in an amount of about 0.8%, and anunidentified byproduct. The product was collected by flowing the reactorexit gases through a 20-60 wt % aq. KOH scrubber solution and thentrapping the exit gases from the scrubber into a cylinder kept in dryice or liquid N₂. The product, 1233xf was then substantially isolated bydistillation. Using only Cr₂O₃ catalyst, a selectivity of about 68% to1233xf at a conversion level of about 79% was achieved.

Examples 9A-9D Direct Liquid-Phase Catalytic Fluorination of CCl₃CCl═CH₂with HF to CF₃CFClCH₃ (244-Isomer) Example 9A

About 327 grams HF, about 50 grams CCl₃CCl═CH₂, and about 75 grams SbCl₅were charged into a 1-L autoclave. The reaction mixture was stirred atabout 80° C. for about 3 hours under about 610 psig of pressure. Afterthe reaction, the reactor was cooled to about 40° C. and about 300 mlwater was then added slowly into the autoclave over a period of about 45min. After complete addition of water under stirring, the reactor wascooled to about room temperature and then the overhead gases weretransferred to another collecting cylinder. The yield of CF₃CFClCH₃ wasabout 89% at a CCl₃CCl═CH₂ conversion level of about 88%. The othermajor by-products were CF₃CF₂CH₃ (2%), and an unidentified isomer of aC4 compound of the general formula, C₄H₃Cl₃F₄ (8%).

Example 9B

About 327 grams HF, about 50 grams CCl₃CCl═CH₂, and about 75 grams SbCl₅were charged into a 1-L autoclave. The reaction mixture was stirred atabout 100° C. for about 3 hours under about 685 psig of pressure. Afterthe reaction, the reactor was cooled to about 40° C. and about 300 mlwater was then added slowly into the autoclave over a period of about 45minutes. After complete addition of water under stifling, the reactorwas cooled to room temperature and then the overhead gases weretransferred to another collecting cylinder. The yield of CF₃CFClCH₃ wasabout 78% at a CCl₃CCl═CH₂ conversion level of about 100%. The othermajor by-products were CF₃CF₂CH₃ (about 4%), and an unidentified isomerof a C4 compound of the general formula, C₄H₃Cl₃F₄ (about 13%).

Example 9C

About 327 grams HF, about 50 grams CCl₃CCl═CH₂, and about 75 grams SbCl5were charged into a 1-L autoclave. The reaction mixture was stirred atabout 125° C. for about 6 hours under about 825 psig of pressure. Afterthe reaction, the reactor was cooled to about 40° C. and about 300 mlwater was then added slowly into the autoclave over a period of about 45min. After complete addition of water under stifling, the reactor wascooled to about room temperature and then the overhead gases weretransferred to another collecting cylinder. The major products wereCF₃CF₂CH₃ (about 53%) and CF₃CFClCH₃ (about 25%) at a CCl₃CCl═CH₂conversion level of about 100%. The other major by-products were andunidentified isomer of a C4 compound of the general formula, C₄H₃Cl₃F₄(8%) and tar.

Example 9D

About 327 grams HF, about 50 grams CCl₃CCl═CH₂, and about 75 g SbCl₅were charged into a 1-L autoclave. The reaction mixture was stirred atabout 150° C. for about 6 hours under about 825 psig of pressure. Afterthe reaction, the reactor was cooled to about 40° C. and about 300 mlwater was then added slowly into the autoclave over a period of about 45minutes. After complete addition of water under stifling, the reactorwas cooled to about room temperature and then the overhead gases weretransferred to another collecting cylinder. The major products wereCF₃CF₂CH₃ (about 57%) and CF₃CFClCH₃ (about 15%) at a CCl₃CCl═CH₂conversion level of about 100%. The other major by-products were andunidentified isomer of a C4 compound of the general formula, C₄H₃Cl₃F₄(about 11%) and tar.

Example 10 Catalytic Conversion of CF₃CF₂CH₃ to CF₃CF═CH₂

A 22-inch (½-inch diameter) Monel tube gas phase reactor was chargedwith 120 cc of a catalyst. The reactor was mounted inside a heater withthree zones (top, middle and bottom). The reactor temperature was readby custom made 5-point thermocouples kept at the middle inside of thereactor. The inlet of the reactor was connected to a pre-heater, whichwas kept at about 300° C. by electrical heating. Organic material(245cb) was fed from a cylinder kept at about 65° C. through aregulator, needle valve, and a gas mass-flow-meter. The organic line tothe pre-heater was heat traced and kept at a substantially constanttemperature in a range of from about 65° C. to about 70° C. byelectrical heating to avoid condensation. The feed cylinder was mountedon a scale to monitor its weight by difference. The reactions were runat a substantially constant reactor pressure of from about 0 to about100 psig by controlling the flow of reactor exit gases by anotherresearch control valve. The gas mixtures exiting reactor was analyzed byon-line GC and GC/MS connected through a hotbox valve arrangements toprevent condensation. The conversion of 245cb was in the range of fromabout 30% to about 70% and the selectivity to 1234yf was in the range offrom about 90% 5o about 100% depending on the reaction conditions. Theproducts were collected by flowing the reactor exit gases through a20-60-wt % of aq. KOH scrubber solution and then trapping the exit gasesfrom the scrubber into a cylinder kept in dry ice or liquid N₂. Theproducts were then substantially isolated by distillation. Results aretabulated in Table 4.

TABLE 4 Transformation of CF₃CF₂CH₃ to 1234yf T, H₂, CF₃CF₂CH₃ (245cb)Conversion of 1234yf # Cat ° C. sccm sccm 245cb, % (Sel. %) 1 A 575 0 6579 63 2 B 575 0 68 82 57 3 C 575 0 73 73 61 4 D 575 0 68 84 59 5 D 57520 68 89 73 6 E 550 0 69 92 53 7 F 550 0 67 93 33 8 G 550 0 69 73 46Reaction conditions: pressure, 2.5-5.3 psig; catalyst, 100 cc, A isNORIT RFC 3; B is Shiro-Saga activated carbon; C is Aldrich activatedcarbon; D is Calgon activated carbon; E is 0.5 wt % Pd/C; F is 0.5 wt %Pt/C; G is Ni-mesh; Organic cylinder temperature is about 65° C.;CF₃CF₂CH₃ (245cb) line to the preheater is maintained at about 50° C.;preheater temperature is maintained at about 350° C.; N₂ flow is notused; pressure is maintained at about 3 psig.

Having thus described a few particular embodiments of the invention,various alterations, modifications, and improvements will readily occurto those skilled in the art. Such alterations, modifications, andimprovements, as are made obvious by this disclosure, are intended to bepart of this description though not expressly stated herein, and areintended to be within the spirit and scope of the invention.Accordingly, the foregoing description is by way of example only, andnot limiting.

What is claimed is:
 1. A method for producing fluorinated organiccompounds comprising fluorinating at least a first compound of Formula(I)C(X)mCCl(Y)nC(X)m  (I) to form at least one compound of Formula (IB):C(X)₃CClYC(X)₃  (IB), and dehydrohalogenating the at least one compoundof Formula (IB) to form to at least one compound of Formula (II)CF₃CF═CHZ  (II) where each X, Y and Z is independently H, F, Cl, I orBr, and each m is independently 1, 2 or 3, and n is 0 or
 1. 2. Themethod of claim 1 wherein said fluorinating step is an indirectconverting step.
 3. The method of claim 1 wherein said at least onefirst compound of Formula (I) comprises a compound wherein n is 0, eachX is independently H or Cl, and Z is H.
 4. The method of claim 1 whereinsaid at least one first compound of Formula (I) comprises a compoundFormula (IA):C(X)₂═CClC(X)₃  (IA) wherein X is as identified in claim
 1. 5. Themethod of claim 4 wherein Z in said compound of Formula (II) is H. 6.The method of claim 4 wherein X is independently H or Cl.
 7. The methodof claim 1 wherein said at least one first compound of Formula (I)comprises at least one tetrachloropropene.
 8. The method of claim 4wherein said at least one first compound of Formula (IA) comprises atleast one tetrachloropropene.
 9. The method of claim 1 wherein said atleast one first compound of Formula (I) comprises CH₂═CClCCl₃.
 10. Themethod of claim 1 wherein said at least one first compound of Formula(I) comprises CCl₂═CClCH₂Cl.
 11. The method of claim 1 wherein said atleast one first compound of Formula (I) comprises CHCl═CClCCl₂H.
 12. Themethod of claim 1 wherein said at least one first compound of Formula(I) is selected from the group consisting of CH₂═CClCCl₃, CCl2=CClCH₂Cl,CHCl═CClCCl₂H, and combinations of these.
 13. The method of claim 1wherein said at least one first compound of Formula (I) comprises acompound wherein n is 0 and the terminal saturated carbon has three (3)F substituents.
 14. The method of claim 1 wherein said at least onefirst compound of Formula (I) comprises a compound Formula (IAA):C(X)₂═CClCF₃  (IAA) wherein X is as identified in claim
 1. 15. Themethod of claim 14 wherein each X in said compound of Formula (IAA) isindependently H or Cl.
 16. The method of claim 1 wherein said at leastone first compound of Formula (I) comprises at least onetrifluoropropene.
 17. The method of claim 16 wherein said at least onetrifluoropropene comprises CH₂═CClCF₃ (HCFO-1233xf).
 18. The method ofclaim 1 wherein each X in said compound of Formula (IB) is independentlyH, F, or Cl.
 19. The method of claim 1 wherein said Formula (IB)compound has at least two halogens on one terminal carbon and at leasttwo hydrogen atoms on the other terminal carbon.
 20. The method of claim1 wherein said at least one compound of Formula (IB) comprises at leastone propane having at least four halogens substituents.
 21. The methodof claim 20 wherein said at least one compound of Formula (IB) comprisesat least one propane having at least five halogen substituents.
 22. Themethod of claim 1 wherein Y is F and all three X on one terminal carbonare F in said at least one compound of Formula (IB).
 23. The method ofclaim 1 wherein said at least one compound of Formula (IB) comprises atetra-fluorinated, mono-chlorinated propane.
 24. The method of claim 23wherein said at least one tetra-fluorinated, mono-chlorinated propanecomprises 1,1,1,2-tetrafluoro-2-chloropropane.